EP0093993B1 - Agent in powder form for reducing the flammability of combustible materials - Google Patents

Agent in powder form for reducing the flammability of combustible materials Download PDF

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Publication number
EP0093993B1
EP0093993B1 EP83104304A EP83104304A EP0093993B1 EP 0093993 B1 EP0093993 B1 EP 0093993B1 EP 83104304 A EP83104304 A EP 83104304A EP 83104304 A EP83104304 A EP 83104304A EP 0093993 B1 EP0093993 B1 EP 0093993B1
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Prior art keywords
agent
mass
ammonium polyphosphate
beckopox
viscosity
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German (de)
French (fr)
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EP0093993A1 (en
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Horst Dr. Staendeke
Franz-Josef Dr. Dany
Joachim Dr. Kandler
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/92—Fire or heat protection feature
    • Y10S428/921—Fire or flameproofing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/906—Polyurethane cellular product containing unreacted flame-retardant material

Definitions

  • the invention relates to a particulate agent based on free-flowing, powdery ammonium polyphosphates for reducing the flammability of combustible substances.
  • German Auslegeschrift 1283532 describes a process for the production of flame-retardant polyurethanes from high molecular weight polyhydroxyl compounds, polyisocyanates and catalysts, an ammonium polyphosphate of the general formula in which n is an integer with an average value above 10, m is an integer up to a maximum of n + 2 and m / n is between approximately 0.7 and 1.1, as a flame retardant additive is proposed.
  • ammonium polyphosphates of the aforementioned general formula give the latter good flame retardancy when used in polyurethanes, they have the disadvantage that they are not sufficiently water-insoluble and are therefore washed out of the plastic over time by weather conditions.
  • the ammonium polyphosphates described there as practically water-insoluble nevertheless have a considerable solubility in water by dissolving up to 5 g of the ammonium polyphosphate in 10 m of the ammonium polyphosphate in 100 m 3 of water at 25 ° C. are, ie that the soluble proportions of the ammonium polyphosphate amount to up to 50% of the amount used.
  • the agent of the invention generally has an average particle size of about 0.01 to 0.05 mm and the degree of condensation n of the ammonium polyphosphate is preferably an integer with an average value of 450 to 800, determined by the end group tritation method (from Wazer ), Griffiter and McCullough, Anal. Chem. 26, p. 1755 (1954).
  • the proportion of the epoxy resin is 1 to 5% by mass.
  • the epoxy resin is primarily an alcohol-soluble, curable resin which arises from the reaction of a dihydric or polyhydric alcohol with epichlorohydrin or glycerol dichlorohydrin under alkaline conditions or, if appropriate, in the presence of an acid catalyst and subsequent alkali treatment.
  • the invention also relates to the use of the above-described agent for flame retarding polyurethanes or polyurethane foams, the content of the agent in the polyurethane foam being about 5 to 25% by mass, based on the amount of the polyol component of the polyurethane.
  • the epoxy resins can be applied to the ammonium polyphosphate particles either in an alcoholic resin solution by curing the resin with the aid of a hardener while stirring the ammonium polyphosphate / resin suspension or by evaporating the solvent of the suspension in a heated kneader while simultaneously curing the resin.
  • the inventive coating of the ammonium polyphosphate particles with a hardened epoxy resin the solubility of the ammonium polyphosphate in water is significantly reduced, which has a favorable effect, for. B. when using a pretreated ammonium polyphosphate as a flame retardant in polyurethane foams.
  • the addition of the agent according to the invention to the starting mixture for the formation of polyurethane foam for the purpose of flame protection does not affect its viscosity in the sense of an increase in viscosity, so that starting mixtures of this type can be processed without difficulty.
  • epoxy resins are distinguished by the fact that they outperform the known resins in the desired reduction in solubility in water and in the reduction of viscosity in an aqueous medium.
  • ammonium polyphosphate (®Exolit 263) were suspended in 600 ml of methanol in a glass stirring apparatus and the suspension was heated to a low boil.
  • a methanolic epoxy resin / epoxy hardener solution which had been prepared by dissolving 3 g @ Beckopox EP 128 and 3 g @ Beckopox VEH 2130 in 100 ml of methanol was then added dropwise over the course of 15 minutes. To harden the epoxy resin, the suspension was stirred for 2 hours while gently boiling the methanol. After cooling, the mixture was filtered and the filter cake obtained was dried at 110 ° C. in a stream of nitrogen. 154 g of treated ammonium polyphosphate with an epoxy resin content of 3.5% by mass were obtained.
  • Example 2 The procedure was analogous to Example 1, but a solution of 3 g of ®Beckopox VEP 22 and 3 g of ®Beckopox VEH 2130 in 100 ml of methanol was used. 152 g of treated ammonium polyphosphate, hereinafter called APP, with an epoxy resin content of 3.6% by mass were obtained.
  • APP treated ammonium polyphosphate
  • Example 2 The procedure was analogous to Example 3, but using 200 ml of butanol as the solvent for the epoxy resin / epoxy hardener system. 200 g of resin-containing APP with an epoxy resin content of 1.0% by mass were obtained. The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 2.
  • Example 10 The procedure was analogous to Example 10, except that 3.12 g of ®Beckopox EP 140 and 1.89 g of ®Beckopox EH 641, dissolved in 50 ml of methanol, were used. The yield was 204 g and the epoxy resin content in the APP was 2.4 mass%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The disclosure relates to a particulate agent based on free-flowing, pulverulent ammonium polyphosphate of the general formula H(n-M)+2(NH4)mPnO3n+1 in which n stands for a whole number with an average value of about 20 to 800 and the ratio of m/n is about 1. The agent reduces the ignitability of combustible substances and constists of (a) about 80 to 99.5 mass % ammonium polyphosphate and (b) about 0.5 to 20 mass % hardened epoxide resin having an epoxide equivalent weight of about 170 to about 220, the epoxide resin enveloping the individual ammonium polyphosphate particles.

Description

Gegenstand der Erfindung ist ein teilchenförmiges Mittel auf der Basis von freifliessenden, pulverförmigen Ammoniumpolyphosphaten zur Verminderung der Entzündlichkeit von brennbaren Stoffen.The invention relates to a particulate agent based on free-flowing, powdery ammonium polyphosphates for reducing the flammability of combustible substances.

Es ist generell bekannt, Ammoniumpolyphosphate als Flammschutzmittel für Kunststoffe zu verwenden. Beispielsweise beschreibt die Deutsche Auslegeschrift 1283532 ein Verfahren zur Herstellung von flammwidrigen Polyurethanen aus hochmolekularen Polyhydroxylverbindungen, Polyisocyanaten und Katalysatoren, wobei ein Ammoniumpolyphosphat der allgemeinen Formel

Figure imgb0001
in der n eine ganze Zahl mit einem über 10 liegenden Durchschnittswert ist, m eine ganze Zahl bis maximal n+2 bedeutet und m/n zwischen etwa 0,7 und 1,1 liegt, als Flammschutzmittelzusatz vorgeschlagen wird.It is generally known to use ammonium polyphosphates as flame retardants for plastics. For example, German Auslegeschrift 1283532 describes a process for the production of flame-retardant polyurethanes from high molecular weight polyhydroxyl compounds, polyisocyanates and catalysts, an ammonium polyphosphate of the general formula
Figure imgb0001
 in which n is an integer with an average value above 10, m is an integer up to a maximum of n + 2 and m / n is between approximately 0.7 and 1.1, as a flame retardant additive is proposed.

Obgleich Ammoniumpolyphosphate der vorgenannten allgemeinen Formel beim Einsatz in Polyurethanen letzteren einen guten Flammschutzverleihen, sind sie mit dem Nachteil behaftet, dass sie nicht ausreichend wasserunlöslich sind und deshalb im Laufe der Zeit durch Witterungseinflüsse aus dem Kunststoff ausgewaschen werden. Wie aus Spalte 3 der DE-AS 1283532 ersichtlich, besitzen die dort als praktisch wasserunlöslich bezeichneten Ammoniumpolyphosphate dennoch eine beachtliche Löslichkeit in Wasser, indem beim Aufschlämmen von 10 g des Ammoniumpolyphosphats in 100 m3 Wasser bei 25° C bis zu 5 g des Ammoniumpolyphosphates gelöst werden, d.h. dass die löslichen Anteile des Ammoniumpolyphosphates bis zu 50% der eingesetzten Menge betragen.Although ammonium polyphosphates of the aforementioned general formula give the latter good flame retardancy when used in polyurethanes, they have the disadvantage that they are not sufficiently water-insoluble and are therefore washed out of the plastic over time by weather conditions. As can be seen from column 3 of DE-AS 1283532, the ammonium polyphosphates described there as practically water-insoluble nevertheless have a considerable solubility in water by dissolving up to 5 g of the ammonium polyphosphate in 10 m of the ammonium polyphosphate in 100 m 3 of water at 25 ° C. are, ie that the soluble proportions of the ammonium polyphosphate amount to up to 50% of the amount used.

Bei der Herstellung selbstverlöschender, nachgiebiger Polyurethanschäume, beispielsweise nach dem Verfahren der DE-AS 2313819, durch Polykondensation eines Trimethylpropan eingebaut enthaltenden Polyester-Polyols mit einem organischen Polyisocyanat in Gegenwart von mindestens 10 Gewichtsteilen Ammoniumpolyphosphat, bezogen auf 100 Gewichtsteile des Polyols, bereitet die Homogenisierung des Ausgangsgemisches aufgrund dessen Viskosität besondere Schwierigkeiten. In Gegenwart von 30 Gew.-% Ammoniumpolyphosphat mit einem Kondensationsgrad n von etwa 700 beträgt nämlich die Viskosität des Ansatzes etwa 70 000 mPa.s, so dass das Rühren oder Kneten des Ansatzes problematisch ist, weil bereits die Viskosität eines in der Praxis eingesetzten Polyester-polyols auf der Basis von Adipinsäure, Diethylenglykol und einem Triol bei 25°C über 20 000 mPa.s liegt. In diesem Falle war man bisher genötigt ein Ammoniumpolyphosphat mit niedrigem Kondensationsgrad von n <400 zu verwenden, das jedoch eine höhere Wasserlöslichkeit besitzt als die hochkondensierten Phosphate und dadurch aus dem Schaumstoff bei Bewitterung teilweise ausgewaschen wird.In the production of self-extinguishing, flexible polyurethane foams, for example by the process of DE-AS 2313819, by polycondensation of a trimethylpropane-containing polyester polyol with an organic polyisocyanate in the presence of at least 10 parts by weight of ammonium polyphosphate, based on 100 parts by weight of the polyol, the homogenization of the Starting mixture due to its viscosity, special difficulties. In the presence of 30 wt .-% ammonium polyphosphate with a degree of condensation n of about 700, the viscosity of the batch is about 70,000 mPa.s, so that stirring or kneading the batch is problematic because the viscosity of a polyester used in practice -polyols based on adipic acid, diethylene glycol and a triol at 25 ° C is over 20,000 mPa.s. In this case, it was previously necessary to use an ammonium polyphosphate with a low degree of condensation of n <400, which, however, has a higher water solubility than the highly condensed phosphates and is therefore partially washed out of the foam during weathering.

Es bestand somit die Aufgabe, Mittel und Wege zur Verminderung der Löslichkeit von Ammoniumpolyphosphaten in Wasser zu finden, so dass die Gefahr des Auswaschens des Ammoniumpolyphosphates beim Einsatz als Flammschutzmittel in Kunststoffen durch Witterungseinflüsse möglichst weitgehend vermieden wird. Weiterhin soll der Zusatz des Ammoniumpolyphosphates in bereits viskose Polyesterpolyole die Viskosität des Ansatzes so wenig wie möglich erhöhen.It was therefore the task of finding ways and means of reducing the solubility of ammonium polyphosphates in water, so that the risk of washing out the ammonium polyphosphate when used as a flame retardant in plastics as a result of weather influences is avoided as far as possible. Furthermore, the addition of the ammonium polyphosphate in already viscous polyester polyols should increase the viscosity of the batch as little as possible.

Die vorstehende erläuterte Aufgabe wird auch in den Deutschen Offenlegungsschriften 2949537 und 3005252 zu lösen versucht, indem die Ammoniumpolyphosphat-Teilchen mit einem Melaminharz bzw. einem gehärteten Phenolharz behandelt und umhüllt werden.The above-mentioned task is also attempted in German Offenlegungsschriften 2949537 and 3005252 by treating and encasing the ammonium polyphosphate particles with a melamine resin or a hardened phenolic resin.

Es hat sich nunmehr gezeigt und war nicht vorhersehbar, dass der erfindungsgemässe Ersatz von Melamin- bzw. Phenolharzen durch Epoxidharze mit gewissen Vorteilen verbunden ist.It has now been shown and was not foreseeable that the replacement of melamine or phenolic resins by epoxy resins according to the invention is associated with certain advantages.

Somit betrifft die Erfindung ein teilchenförmiges Mittel auf der Basis von freifliessenden, pulverförmigen Ammoniumpolyphosphaten der allgemeinen Formel

Figure imgb0002
in welcher n eine ganze Zahl mit einem Durchschnittswert von etwa 20 bis 800 bedeutet und das Verhältnis von m zu n etwa 1 beträgt, zur Verminderung der Entzündlichkeit von brennbaren Stoffen, welches dadurch gekennzeichnet ist, dass es aus

  • a) etwa 80 bis 99,5 Masse% Ammoniumpolyphosphat und
  • b) etwa 0,5 bis 20 Masse% eines gehärteten Epoxidharzes mit einem Epoxid-Äquivalentgewicht von etwa 170 bis etwa 220, wobei das Epoxidharz die einzelnen Ammoniumpolyphosphatteilchen umhüllt,

besteht.The invention thus relates to a particulate agent based on free-flowing, powdery ammonium polyphosphates of the general formula
Figure imgb0002
 in which n is an integer with an average value of approximately 20 to 800 and the ratio of m to n is approximately 1, for reducing the flammability of combustible substances, which is characterized in that it consists of
  • a) about 80 to 99.5 mass% ammonium polyphosphate and
  • b) about 0.5 to 20% by mass of a hardened epoxy resin with an epoxy equivalent weight of about 170 to about 220, the epoxy resin encasing the individual ammonium polyphosphate particles,

consists.

Das Mittel der Erfindung besitzt im allgemeinen eine mittlere Teilchengrösse von etwa 0,01 bis 0,05 mm und der Kondensationsgrad n des Ammoniumpolyphosphates ist vorzugsweise eine ganze Zahl mit einem Durchschnittswert von 450 bis 800, bestimmt nach dem Endgruppen-Tritations-Verfahren (von Wazer), Griffiter und McCullough, Anal. Chem. 26, S. 1755 (1954).The agent of the invention generally has an average particle size of about 0.01 to 0.05 mm and the degree of condensation n of the ammonium polyphosphate is preferably an integer with an average value of 450 to 800, determined by the end group tritation method (from Wazer ), Griffiter and McCullough, Anal. Chem. 26, p. 1755 (1954).

Entsprechend einer weiteren bevorzugten Ausführungsform des erfindungsgemässen Mittels beträgt der Anteils des Epoxidharzes 1 bis 5 Masse%.According to a further preferred embodiment of the agent according to the invention, the proportion of the epoxy resin is 1 to 5% by mass.

Das Epoxidharz istvornehmlich ein alkohollösliches, härtbares Harz, welches durch Reaktion eines zweiwertigen oder mehrwertigen Alkohols mit Epichlorhydrin oder Glycerindichlorhydrin unter alkalischen Bedingungen oder gegebenenfalls in Gegenwart eines sauren Katalysators und anschliessender Alkali-Behandlung entsteht.The epoxy resin is primarily an alcohol-soluble, curable resin which arises from the reaction of a dihydric or polyhydric alcohol with epichlorohydrin or glycerol dichlorohydrin under alkaline conditions or, if appropriate, in the presence of an acid catalyst and subsequent alkali treatment.

Schliesslich betrifft die Erfindung auch die Verwendung des vorbeschriebenen Mittels zum Flammfestmachen von Polyurethanen bzw. Polyurethanschäumen, wobei der Gehalt des Mittels im Polyurethanschaum etwa 5 bis 25 Masse%, bezogen auf die Menge der Polyolkomponente des Polyurethans, beträgt.Finally, the invention also relates to the use of the above-described agent for flame retarding polyurethanes or polyurethane foams, the content of the agent in the polyurethane foam being about 5 to 25% by mass, based on the amount of the polyol component of the polyurethane.

Das Aufbringen der Epoxidharze auf die Ammoniumpolyphosphat-Teilchen kann entweder in einer alkoholischen Harzlösung durch Aushärten des Harzes mit Hilfe eines Härters unter Rühren der Ammoniumpolyphosphat/Harz-Suspension oder durch Verdampfen des Lösungsmittels der Suspension in einem beheizten Kneter unter gleichzeitiger Härtung des Harzes erfolgen.The epoxy resins can be applied to the ammonium polyphosphate particles either in an alcoholic resin solution by curing the resin with the aid of a hardener while stirring the ammonium polyphosphate / resin suspension or by evaporating the solvent of the suspension in a heated kneader while simultaneously curing the resin.

Durch die Erfindungsgemässe Umhüllung der Ammoniumpolyphosphat-Teilchen mit einem gehärteten Epoxidharz wird die Löslichkeit des Ammoniumpolyphosphates in Wasser erheblich herabgesetzt, was sich günstig auswirkt, z. B. beim Einsatz eines derartig vorbehandelten Ammoniumpolyphosphates als Flammschutzmittel in Polyurethanschäumen.The inventive coating of the ammonium polyphosphate particles with a hardened epoxy resin, the solubility of the ammonium polyphosphate in water is significantly reduced, which has a favorable effect, for. B. when using a pretreated ammonium polyphosphate as a flame retardant in polyurethane foams.

Darüberhinaus beeinflusst der Zusatz des erfindungsgemässen Mittels zu dem Ausgangsgemisch für die Polyurethanschaumbildung zum Zwecke des Flammschutzes nicht dessen Viskosität im Sinne einer Viskositätserhöhung, so dass derartige Ausgangsgemische ohne Schwierigkeiten verarbeitet werden können.In addition, the addition of the agent according to the invention to the starting mixture for the formation of polyurethane foam for the purpose of flame protection does not affect its viscosity in the sense of an increase in viscosity, so that starting mixtures of this type can be processed without difficulty.

Im Vergleich zu den bekannten Umhüllungsharzen, wie Phenol oder Melaminharzen, zeichnen sich Epoxidharze dadurch aus, dass sie die bekannten Harze in der erwünschten Verringerung der Löslichkeit in Wasser sowie der Reduzierung der Viskosität im wässerigem Milieu übertreffen.Compared to the known coating resins, such as phenol or melamine resins, epoxy resins are distinguished by the fact that they outperform the known resins in the desired reduction in solubility in water and in the reduction of viscosity in an aqueous medium.

Die erfindungsgemässen Mittel, deren Herstellung und Vorteile werden in den nachfolgenden Beispielen erläutert. Zur Durchführung der in den Beispielen dargelegten Versuche wurden im Handel erhältliche Ammoniumpolyphosphate sowie verschiedene, ebenfalls handelsübliche Epoxidharz-Systeme eingesetzt. Im einzelnen handelt es sich hierbei um folgende Produkte:

  • 1. ®Exolit 263, Hoechst AG, Frankfurt/Main
    • Es handelt sich um ein feinkörniges, in Wasser schwer lösliches Ammoniumpolyphosphat der Formel (NH4P03)n, wobei n ~ 700 ist.
  • 2. ®Exolit 422, Hoechst AG, Frankfurt/Main
    • Es handelt sich um ein feinkörniges, in Wasser schwer lösliches Ammoniumpolyphosphat, wobei der Kondensationsgrad n ~ 700 ist.
  • 3. @Beckopox EP 128, Hoechst AG, Frankfurt/ Main
    • Flüssiges, sehr niedrig-viskoses Epoxidharz mit einem Epoxidäquivalentgewicht von ca. 200, einer Dichte bei 25°C von 1,12 g/ml und einer dynamischen Viskosität bei 25°C von 500-1000 mPa.s.
  • 4. ®Beckopox VEH 2130, Hoechst AG, Frankfurt/Main
    • Modifizierter aliphatischer Polyaminhärter mit einem H-Äquivalentgewicht von ca. 200, einer Dichte bei 25°C von 1,10 g/ml und einer dynamischen Viskosität bei 25°C von ca. 12000 mPa.s. 5. ®Beckopox VEP 22, Hoechst AG, Frankfurt/ Main
  • Flüssiges, sehr niedrig-viskoses Epoxidharz mit einem Epoxidäquivaientgewichtvonca. 195, einer Dichte bei 25°C von 1,11 g/ml und einer dynamischen Viskosität bei 25°C von 650-700 mPa.s.
  • 6. ®Beckopox EP 140, Hoechst AG, Frankfurt/ Main
    • Flüssiges, mittelviskoses Epoxidharz mit einem Epoxidäquivalentgewicht von ca. 190, einer Dichte bei 25°C von ca. 1,16 g/ml und einer dynamischen Viskosität bei 25°C von 9000-12000 mPa.s.
  • 7. ®Beckopox EH 643, Hoechst AG, Frankfurt/ Main
    • Lösemittelfreier Epoxidharzhärter auf Basis Polyamin mit einem H-Aktiv-Äquivalentgewicht von 55 und einer dynamischen Viskosität bei 25° C von 7000-10000 mPa.s.
  • 8. ®Beckopox EH 641, HoechstAG, Frankfurt/ Main
    • Lösemittelfreier Epoxidharzhärter auf Basis Polyamin mit einem H-Aktiv-Äquivalentgewicht von 114 und einer dynamishen Viskosität bei 25° C von 200-300 mPa.s.
  • 9. @Desmophen 2200, Bayer AG, Leverkusen
    • Wenig verzweigter Polyester auf der Basis von Adipinsäure, Diethylenglykol und einem Triol; Hydroxyzahl 60 mg KOH/g; Viskosität bei 75°C 1000 mPa.s.; Dichte bei 20°C 1,18 g/ml; Wassergehalt < 0,1 Masse%.
    • @Desmophen 2200 dient zur Herstellung von Polyurethanschaumstoff auf Polyesterbasis.
The agents according to the invention, their production and advantages are explained in the examples below. Commercially available ammonium polyphosphates and various, likewise commercially available, epoxy resin systems were used to carry out the experiments set out in the examples. Specifically, these are the following products:
  • 1. ®Exolit 263, Hoechst AG, Frankfurt / Main
    • It is a fine-grained, water-poorly soluble ammonium polyphosphate of the formula (NH 4 P0 3 ) n , where n ~ 700.
  • 2. ®Exolit 422, Hoechst AG, Frankfurt / Main
    • It is a fine-grained, sparingly water-soluble ammonium polyphosphate, the degree of condensation being n ~ 700.
  • 3. @ Beckopox EP 128, Hoechst AG, Frankfurt / Main
    • Liquid, very low-viscosity epoxy resin with an epoxy equivalent weight of approx. 200, a density at 25 ° C of 1.12 g / ml and a dynamic viscosity at 25 ° C of 500-1000 mPa.s.
  • 4. ®Beckopox VEH 2130, Hoechst AG, Frankfurt / Main
    • Modified aliphatic polyamine hardener with an H equivalent weight of approx. 200, a density at 25 ° C of 1.10 g / ml and a dynamic viscosity at 25 ° C of approx. 12000 mPa.s. 5. ®Beckopox VEP 22, Hoechst AG, Frankfurt / Main
  • Liquid, very low-viscosity epoxy resin with an epoxy equivalent weight of approx. 195, a density at 25 ° C of 1.11 g / ml and a dynamic viscosity at 25 ° C of 650-700 mPa.s.
  • 6. ®Beckopox EP 140, Hoechst AG, Frankfurt / Main
    • Liquid, medium-viscosity epoxy resin with an epoxy equivalent weight of approx. 190, a density at 25 ° C of approx. 1.16 g / ml and a dynamic viscosity at 25 ° C of 9000-12000 mPa.s.
  • 7. ®Beckopox EH 643, Hoechst AG, Frankfurt / Main
    • Solvent-free epoxy resin hardener based on polyamine with an H-active equivalent weight of 55 and a dynamic viscosity at 25 ° C of 7000-10000 mPa.s.
  • 8. ®Beckopox EH 641, HoechstAG, Frankfurt / Main
    • Solvent-free epoxy resin hardener based on polyamine with an H-active equivalent weight of 114 and a dynamic viscosity at 25 ° C of 200-300 mPa.s.
  • 9. @ Desmophen 2200, Bayer AG, Leverkusen
    • Little branched polyester based on adipic acid, diethylene glycol and a triol; Hydroxyl number 60 mg KOH / g; Viscosity at 75 ° C 1000 mPa.s .; Density at 20 ° C 1.18 g / ml; Water content <0.1 mass%.
    • @ Desmophen 2200 is used to manufacture polyester-based polyurethane foam.

Beispiel 1:Example 1:

In einer Rührapparatur aus Glas wurden in 600 ml Methanol 150 g Ammoniumpolyphosphat (®Exolit 263) suspendiert und die Suspension zum schwachen Sieden erhitzt. Dann wurde im Verlauf von 15 Min. eine methanolische Epoxidharz/Epoxidhärter-Lösung eingetropft, die durch Auflösen von 3 g @Beckopox EP 128 und 3 g @Beckopox VEH 2130 in 100 ml Methanol hergestellt worden war. Zur Härtung des Epoxidharzes wurde die Suspension 2 Stunden unter schwachem Sieden des Methanols gerührt. Nach dem Abkühlen wurde filtriert und der erhaltene Filterkuchen bei 110°C im Stickstoffstrom getrocknet. Es wurden 154 g behandeltes Ammoniumpolyphosphat mit einem Epoxidharzgehalt von 3,5 Masse% erhalten.150 g of ammonium polyphosphate (®Exolit 263) were suspended in 600 ml of methanol in a glass stirring apparatus and the suspension was heated to a low boil. A methanolic epoxy resin / epoxy hardener solution which had been prepared by dissolving 3 g @ Beckopox EP 128 and 3 g @ Beckopox VEH 2130 in 100 ml of methanol was then added dropwise over the course of 15 minutes. To harden the epoxy resin, the suspension was stirred for 2 hours while gently boiling the methanol. After cooling, the mixture was filtered and the filter cake obtained was dried at 110 ° C. in a stream of nitrogen. 154 g of treated ammonium polyphosphate with an epoxy resin content of 3.5% by mass were obtained.

Zur Bestimmung des Einflusses vorgenannten Produktes auf die Viskosität von ®Desmophen 2200 wurden 30 g des Produktes in 70 g ®Desmophen 2200 eingerührt und ca. 1 Std. bei 25° C temperiert. Anschliessend erfolgte die Viskositätsmessung des Gemisches mit dem Brookfield-Viskosimeter RVT, Spindel C bei 5 Umdrehungen pro Minute. Das Ergebnis ist in Tabelle 1 dargestellt.To determine the influence of the aforementioned product on the viscosity of ®Desmophen 2200, 30 g of the product were stirred into 70 g of ®Desmophen 2200 and heated at 25 ° C. for about 1 hour. The viscosity of the mixture was then measured using the Brookfield RVT, spindle C at 5 revolutions per minute. The result is shown in Table 1.

Zur Bestimmung der wasserlöslichen Anteile wurden 10 g des hergestellten Produktes in 100 ml Wasser suspendiert und die Suspension 20 min bei 25° C gerührt. Anschliessend wurde der im Wasser ungelöste Anteil des Produktes innerhalb von 40 min durch Zentrifugieren sedimentiert. Von der überstehenden klaren Lösung wurden 5,0 ml in eine zuvor gewogene Aluminiumschale pipettiert und bei 120°C im Trockenschrank eingedampft. Aus der Menge des Verdampfungsrückstandes wurde der wasserlösliche Anteil berechnet. Das Ergebnis ist in Tabelle 1 dargestellt.To determine the water-soluble fractions, 10 g of the product produced were suspended in 100 ml of water and the suspension was stirred at 25 ° C. for 20 minutes. The undissolved portion of the product was then sedimented by centrifugation within 40 min. 5.0 ml of the supernatant clear solution were pipetted into a previously weighed aluminum dish and evaporated at 120 ° C. in a drying cabinet. The water-soluble fraction was calculated from the amount of the evaporation residue. The result is shown in Table 1.

Beispiel 2:Example 2:

Es wurde analog Beispiel 1 verfahren, wobei jedoch eine Lösung von 3 g ®Beckopox VEP 22 und 3 g ®Beckopox VEH 2130 in 100 ml Methanol eingesetzt wurde. Es wurden 152 g behandeltes Ammoniumpolyphosphat, im Folgenden APP genannt, mit einem Epoxidharzgehalt von 3,6 Masse% erhalten.The procedure was analogous to Example 1, but a solution of 3 g of ®Beckopox VEP 22 and 3 g of ®Beckopox VEH 2130 in 100 ml of methanol was used. 152 g of treated ammonium polyphosphate, hereinafter called APP, with an epoxy resin content of 3.6% by mass were obtained.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 1 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 1.

Beispiel 3:Example 3:

In den 1 I-Kolben eines Labor-Rotationsverdampfers wurden 200 g APP (@Exolit 263) eingewogen und das APP mit einer Lösung aus 1,55 g ®Beckopox EP 140 und 0,45 g @Beckopox EH 643 in 140 ml Methanol versetzt. Unter schwachem Unterdruck von ca. 0,95 bar wurde 1 Std. bei ca. 60°C gehärtet und anschliessend das Methanol unter vermindertem Druck bei ca. 0,85 bar abdestilliert. Die Trocknung des Produkts erfolgte bei 110° C/0,1 bar. Es wurden 200 g harzhaltiges APP mit einem Epoxidharzgehalt von 1,0 Masse% erhalten.200 g of APP ( @ Exolit 263) were weighed into the 1 liter flask of a laboratory rotary evaporator and a solution of 1.55 g of ®Beckopox EP 140 and 0.45 g of @ Beckopox EH 643 in 140 ml of methanol was added to the APP. Curing was carried out at 60 ° C. for 1 hour under a weak vacuum of approx. 0.95 bar and then the methanol was distilled off under reduced pressure at approx. 0.85 bar. The product was dried at 110 ° C / 0.1 bar. 200 g of resin-containing APP with an epoxy resin content of 1.0% by mass were obtained.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 2 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 2.

Beispiel 4:Example 4:

Es wurde analog Beispiel 3 verfahren, wobei jedoch als Lösungsmittel für das Epoxidharz/ Epoxidhärter-System 200 ml Butanol eingesetzt wurden. Es wurden 200 g harzhaltiges APP mit einem Epoxidharzgehaltvon 1,0 Masse% erhalten. Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 2 aufgeführt.The procedure was analogous to Example 3, but using 200 ml of butanol as the solvent for the epoxy resin / epoxy hardener system. 200 g of resin-containing APP with an epoxy resin content of 1.0% by mass were obtained. The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 2.

Beispiel 5:Example 5:

In einem beheizten Laborkneter wurden 200 g APP (®Exolit 263) auf 100° C erwärmt und in Verlauf von 15 min mit einer Lösung aus 7,74 g ®Beckopox EP 140 und 2,26 g @Beckopox EH 643 in 100 ml Methanol versetzt. Anschliessend wurde das Gemisch 1 Std. bei 100-110°C unter Verdampfung des Lösungsmittels und Härtung des Epoxidharzes geknetet. Die Ausbeute betrug 204 g und der Epoxidharzanteil im APP 4,9 Masse%.200 g of APP (®Exolit 263) were heated to 100 ° C. in a heated laboratory kneader and a solution of 7.74 g of ®Beckopox EP 140 and 2.26 g of @ Beckopox EH 643 in 100 ml of methanol was added over the course of 15 minutes . The mixture was then kneaded for 1 hour at 100-110 ° C. with evaporation of the solvent and curing of the epoxy resin. The yield was 204 g and the epoxy resin content in the APP was 4.9 mass%.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 3 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 3.

Beispiel 6:Example 6:

Es wurde analog Beispiel 5 verfahren, wobei jedoch 3,87 g @Beckopox EP 140 und 1,13 g ®Beckopox EH 643 eingesetzt wurden. Die Ausbeute betrug 200 g und der Epoxidharzanteil im APP 2,5 Masse%.The procedure was analogous to Example 5, except that 3.87 g @ Beckopox EP 140 and 1.13 g ®Beckopox EH 643 were used. The yield was 200 g and the epoxy resin content in the APP was 2.5% by mass.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 3 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 3.

Beispiel 7:Example 7:

Es wurde analog Beispiel 5 verfahren, wobei jedoch 1,94 g ®Beckopox EP 140 und 0,57 g ®Beckopox 643 gelöst in 50 ml Methanol eingesetzt wurden. Die Ausbeute betrug 195 g und der Epoxidharzanteil im APP 1,3 Masse%.The procedure was analogous to Example 5, but 1.94 g of ®Beckopox EP 140 and 0.57 g of ®Beckopox 643 dissolved in 50 ml of methanol were used. The yield was 195 g and the epoxy resin content in the APP was 1.3% by mass.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 3 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 3.

Beispiel 8:Example 8:

Es wurde analog Beispiel 5 verfahren, wobei jedoch 0,97 g @Beckopox EP 140 und 0,29g ®Beckopox EH 643 gelöst in 50 ml Methanol eingesetzt wurden. Die Ausbeute betrug 195 g und der Epoxidharzanteil im APP 0,65 Masse%.The procedure was analogous to Example 5, except that 0.97 g @ Beckopox EP 140 and 0.29 g ®Beckopox EH 643 dissolved in 50 ml methanol were used. The yield was 195 g and the epoxy resin content in the APP was 0.65 mass%.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 3 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 3.

Beispiel 9:Example 9:

Es wurde analog Beispiel 5 verfahren, wobei jedoch 1,55 g @Beckopox EP 140 und 0,45 g ®Beckopox EH 643 gelöst in 50 ml n-Butanol eingesetzt wurden. Die Ausbeute betrug 199 g und der Epoxidharzanteil im APP betrug 1,0 Masse%.The procedure was analogous to Example 5, except that 1.55 g @ Beckopox EP 140 and 0.45 g ®Beckopox EH 643 dissolved in 50 ml n-butanol were used. The yield was 199 g and the epoxy resin content in the APP was 1.0% by mass.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 3 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 3.

Beispiel 10:Example 10:

Es wurde analog Beispiel 5 verfahren, wobei jedoch als APP ®Exolit 422 zusammen mit 6,23 g ®Beckopox EP 140 und 3,77 g ®Beckopox EH 641, gelöst in 100 ml Methanol, eingesetzt wurde. Die Ausbeute betrug 206 g und der Epoxidharzanteil im APP 4,8 Masse%.The procedure was analogous to Example 5, but the APP ®Exolit 422 was used together with 6.23 g ®Beckopox EP 140 and 3.77 g ®Beckopox EH 641, dissolved in 100 ml of methanol. The yield was 206 g and the epoxy resin content in the APP was 4.8% by mass.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 4 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 4.

Beispiel 11:Example 11:

Es wurde analog Beispiel 10 verfahren, wobei jedoch 3,12 g ®Beckopox EP 140 und 1,89 g ®Beckopox EH 641, gelöst in 50 ml Methanol, eingesetzt wurden. Die Ausbeute betrug 204 g und der Epoxidharzanteil im APP 2,4 Masse%.The procedure was analogous to Example 10, except that 3.12 g of ®Beckopox EP 140 and 1.89 g of ®Beckopox EH 641, dissolved in 50 ml of methanol, were used. The yield was 204 g and the epoxy resin content in the APP was 2.4 mass%.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 4 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 4.

Beispiel 12:Example 12:

Es wurde analog Beispiel 10 verfahren, wobei jedoch 1,56 g @Beckopox EP 140 und 0,95 g ®Beckopox EH 641, gelöst in 50 ml Methanol, eingesetzt wurden. Die Ausbeute betrug 203 g und der Epoxidharzanteil im APP 1,2 Masse%.The procedure was analogous to Example 10, except that 1.56 g @ Beckopox EP 140 and 0.95 g ®Beckopox EH 641, dissolved in 50 ml methanol, were used. The yield was 203 g and the epoxy resin content in the APP was 1.2% by mass.

Die ermittelten Werte für die Viskosität und die wasserlöslichen Anteile analog Beispiel 1 sind in Tabelle 4 aufgeführt.The values determined for the viscosity and the water-soluble fractions analogous to Example 1 are listed in Table 4.

Die Tabellenwerte zeigen, dass mit Hilfe der erfindungsgemässen Modifizierungsmittel eine deutliche Reduzierung des Löslichkeitsverhaltens des APP erreicht werden kann. Gleiches gilt für das Viskositätsverhalten des APP in wässrigem Medium, während der gleichzeitigen Verbesserung des Polyol-Viskositätsverhaltens Grenzen gesetzt sind.The table values show that a significant reduction in the solubility behavior of the APP can be achieved with the aid of the modifying agents according to the invention. The same applies to the viscosity behavior of the APP in aqueous Me dium, while the simultaneous improvement of the polyol viscosity behavior limits.

Besonders überraschend war jedoch, dass auch beim sehr gering wasserlöslichen ®Exolit 422 noch eine Verringerung der Wasserlöslichkeit von über 50% möglich war.It was particularly surprising, however, that even with the very slightly water-soluble ®Exolit 422 it was still possible to reduce the water solubility by more than 50%.

Was die Vorteile der Epoxidharze als Modifizierungsmittel für APP im Vergleich zu den bekannten Melamin- und Phenolharzen angeht, so werden diese aus den Tabellen 5 und 6 in Verbindung mit der Graphik ersichtlich. So wird die Löslichkeitsabnahme des APP bei Belegung mit dem Epoxidharz anstelle von Melaminharz um maximal 57% verbessert. Beim Vergleich von Epoxidharz mit Phenolharz ist die Verbesserungsrate noch drastischer. Eine vergleichende graphische Darstellung der erzielten Effekte ist der Zeichnung zu entnehmen, wobei A für Phenolharz, B für Melaminharz und C für Epoxidharz steht.

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
 As far as the advantages of epoxy resins as modifiers for APP compared to the known melamine and phenolic resins are concerned, these can be seen from Tables 5 and 6 in connection with the graphic. The solubility decrease of the APP is improved by a maximum of 57% when coated with the epoxy resin instead of melamine resin. When comparing epoxy resin with phenolic resin, the rate of improvement is even more drastic. A comparative graphic representation of the effects achieved can be seen in the drawing, where A stands for phenolic resin, B for melamine resin and C for epoxy resin.
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007

Claims (6)

1. Particulate agent based on free-flowing pulverulent ammonium polyphosphates of the general formula
Figure imgb0009
in which n stands for a whole number with an average value of about 20 to 800 and the ratio of m/n is about 1, for reducing the ignitability of combustible substances, the agent consisting of
a) about 80 to 99.5 mass% ammonium polyphosphate and
b) about 0.5 to 20 mass% of a hardened epoxide resin having an epoxide equivalent weight of about 170 to about 220, the epoxide resin en- velopping the individual ammonium polyphosphate particles.
2. Agent as claimed in claim 1, wherein the particles have a mean size of about 0.01 to 0.05 mm.
3. Agent as claimed in claim 1 or 2, wherein n is a whole number with an average value of 450 to 800.
4. Agent as claimed in claims 1 to 3, wherein the epoxide resin proportion is 1 to 5 mass%.
5. Agent as claimed in claims 1 to 4, wherein the epoxide resin is an alcohol-soluble, hardenable resin which is obtained by reacting a dihydric or polyhydric alcohol with epichlorhydrin or glycerol dichlorohydrin under alkaline conditions or, if desired, in the presence of an acid catalyst, and then treating it with an alkali.
6. Use of the agent as claimed in claims 1-5 for flameproofing polyurethanes or polyurethane foam plastics, the agent being contained in the polyurethane foam plastics in a proportion of about 5 to 25 mass%, based on the quantity of polyol component in the polyurethane.
EP83104304A 1982-05-12 1983-05-02 Agent in powder form for reducing the flammability of combustible materials Expired EP0093993B1 (en)

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DE19823217816 DE3217816A1 (en) 1982-05-12 1982-05-12 PARTICULATE AGENT TO REDUCE THE FLAMMABILITY OF COMBUSTIBLE SUBSTANCES

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